The Unexpected Stability of Hydrazine Molecules in Hydrous Environment under Pressure*

The incomplete decomposition product of metastable hydrazine (N2H4) instead of the energetically favorable ammonia (NH3) upon decompression is one drawback in applications of energetic material oligomeric hydronitrogens. We explore the stability of hydrazine molecules in hydrazine hydrate (N2H4·H2O) under pressure in diamond anvil cells (DACs) combined with in situ Raman spectroscopy and synchrotron x-ray diffraction (XRD) measurements. The results show that one NH2 branch forms NH3 group by hydrogen bonds between hydrazine and water molecules after the sample crystallizes at 3.2 GPa. The strengthening hydrogen bonds cause the torsion of hydrazine molecules and further dominate a phase transition at 7.2 GPa. Surprisingly, the NN single bonds are strengthened with increasing pressure, which keeps the hydrazine molecules stable up to the ultimate pressure of 36 GPa. Furthermore, the main diffraction patterns show continuous shift to higher degrees in the whole pressure range while some weak lines disappear above 8.2 GPa. The present peak-indexing results of the diffraction patterns with Materials Studio show that the phase transition occurs in the same monoclinic crystal system. Upon decompression, all of the hydrazine molecules extract from hydrazine hydrate crystal at 2.3 GPa, which may provide a new way to purify hydrazine from hydrate.